Resinous compositions containing 4-alkoxy-5 halo-2-hydroxy benzophenones resistant to ultraviolet light



United States Patent 3,192,179 RESINQUS COMPOSITIONS CGNTAINING 4- ALKOXY-S HALO-Z-HYDROXY BENZOPHE- NONES RESISTANT T0 ULTRAVIOLET LIGHT Sydney M. Spatz, Buffalo, and Russell I. Steiner, Williamsville, N.Y., assignors to Allied Chemical Corporation, New York, N.Y., a corporation of New York No Drawing. Filed Apr. 3, 1961, Ser. No. 99,980 11 Claims. '(Cl. 260-4535) This application is a continuation-in-part of our application Serial No. 733,474, filed May 7, 1958, issued as US. Patent 3,126,414.

This invention relates to the stabilization of material subject to deterioration by ultraviolet light. It relates more particularly to compositions resistant to ultraviolet light and to processes for making them.

Many materials are subject to deterioration by ultraviolet light, and considerable research has been devoted to the discovery of compounds which will stabilize them against such action. The problem is complicated by the fact that the materials to be stabilized are of various nature and the stabilizer must not impart other objectionable properties in effecting stabilization. Thus the materials to be stabilized include organic plastics, resins, perfumes, foodstuffs, and the like. Many organic plastics tend to become discolored, pitted, brittle, or otherwise undesirable, under the action of ultraviolet light.

To be effective, a stabilizer should absorb the undesired ultraviolet light without itself undergoing undesirable change (it should be stable); it should be compatible with the material it is to protect; it preferably should be colorless or substantially colorless; it should not interfere with other components of compositions in which it is incorporated (such as, catalysts or other components employed in resinous compositions to be polymerized); and it should be effective in relatively small amounts.

We have discovered that a certain class of derivatives of Z-hydroxy-be-nzophenone, described more fully below, are excellent absorbents for ultraviolet light, especially of the range 350400 mg, and possess a number of other desirable properties, thereby rendering them especially useful as stabilizers for substances sensitive to ultraviolet light.

The Q-hydroxy-benzophenones employed as stabilizers or inhibitors in'accordance with the present invention are 2,4 dihydroxy benzophenones (resbenzophenones) and their 4-alkoXy-derivatives in which the hydrogen atom in the -position, or both the 3- and S-hydrogen atoms, are substituted by bromine or chlorine. Such 2-hydroxybenzophenones have the formula wherein R is selected from the group consisting of hydrogen and alkyl (hydrocarbon alkane),

X is selected from the group consisting of bromine and chlorine and Y is selected from the group consisting of hydrogen, bromine and chlorine.

The alkyl group represented by R includes lower alkyl groups, such as methyl, ethyl, propyl, isopropyl, and the various butyl and amyl groups, as well as higher alkyl groups such as hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl. Those in which the alkyl group contains 1 to 12 carbon atoms are preferred.

"ice

We have discovered that such Z-hydroxy-benzophenone compounds, in which the halogen atoms are in the same benzene nucleus as the hydroxyl groups (that is, in the resorcyl radial) are more effective stabilizing agents for material subject to deterioration by ultraviolet light, and especially unsaturated polyester resinous compositions and polyvinyl ester resins, than are the compounds in which the halogen is in the other benzene nucleus, such as 3'- or 4'-bromo-2,4-dihydroxy-benzophenone.

The compounds employed in accordance with the present invention are especially suitable since they possess the additional advantages of being stable under the con ditions of intended use, contribute little or no color to the composition, and when used with such prepolymers or monomers as polyesters, vinyl esters and the like do not cause premature gelation or retard the subsequent polymerization.

The improved ultraviolet stabilizers employed in accordance with this invention are of particular value when used to protect polyester resins, such as those prepared by reacting an alpha, beta unsaturated polycarboxylic acid with an aliphatic polyhydric compound, and especially a dihydric aliphatic alcohol, and admixing the polyester with a polymerizable ethylen-ically unsaturated compound.

Polyvinyl esters such as polyvinyl chloride, polyvinyl acetate and the like, as well as mixtures, also can be stabilized by the incorporation of minor amounts of the halogenated 2-hydroxybenzophenone compounds of this invention (herein referred to as halogenated resbenzophenones).

The halogenated resbenzophenones are generally compatible with the resinous masses. In most instances only relatively small quantities of the order of 0.01% to 1.0% by Weight of the mass are required to impart stabilizing effects, although amounts ranging from 0.01% to 5% will generally include the optimum concentration of stabilizing agent. The optimum concentration to be employed is not critical and will diifer with the particular application, nature of the material, and thickness of the film. The practical concentration to be employed can be readily determined by trial experiments easily performed by those skilled in this art. However, in no instance is an amount more than 25% by weight required.

In general it is convenient to add the stabilizer in solid form to the warm prepolymeric mass, and to agitate the mixture to eifect solution. At times it may be convenient or desirable to introduce the stabilizer in the form of an aqueous dispersion or solution in an organic solvent. The non-reactive character of these stabilizers is of advantage, since no special care need be exercised in eifecting their incorporation in the light sensitive compositions.

Many of the above 2-hydroxy-benzophenones are new compounds.

Thus the following are new:

WQL

wherein R is selected from the group consisting of hydrogen and alk 1,

Z is selected from the group consisting of bromine and chlorine but is chlorine when R is hydrogen; and

Y is selected from the group consisting of hydrogen,

bromine and chlorine.

The halogenated 2-hydroxy-benzophenones employed as stabilizers in accordance with the present invention can be obtained in various ways. A method which we have found to lead to high yields of halogenated compounds comprises treating the corresponding hydroxy-benzophenone, in solution in a non-reactive solvent (that is, a solvent which does not react with the hydroxy-benzophenone nor with the halogen), with bromine or chlorine, and controlling thetemperature to avoid excessive heating.

Thus we have discovered that both the 5-bromoand 3,5=dibromo 2,4-(dihydroxy-benzophenones can be prepared in excellent yields by adding free bromine to a solution of resbenzophenone in a non-reactive solvent (such as dioxane, a lower dialkylether, chlorobenzene, benzene, glacial acetic acid, chloroacetic acid or mixtures of such solvents) under conditions of strict temperature control. At temperatures below 25 C., and preferably at to 16 C., the S-monobrorno derivatives is obtained in yields of about 90%. At temperatures of to 50 C., and preferably to C., the 3,5-dibromo derivative is obtained in about 90% yields.

The corresponding 5-chloro and 3,5-dichloro derivatives of resbenzophenone can be obtained in an analogous fashion. Higher temperatures are required, however. Thus, by passing gaseous chlorine into a solution of resbenzophenone in a non-reactive solvent maintained at a temperature not exceeding about 40 C, until at least the amount of chlorine required for the chlorination has been absorbed, the said corresponding chlorinated resbenzophenones are obtained in excellent yields.

The 4-alkoxy-2-hydroxy-benzophenones also can be halogenated in like manner, higher temperatures also being required. Thus, the mon-o-halogenation of '2-hydroxy- 4-methoxy-benzophenone' is carried out at 25 to 40 C and its dihalogenation at to about 85 C.

The invention will be illustrated by the following specific examples, but it is to be understood that it is not limited to the details thereof and that changes may be made without departing from the scope of the invention. The temperatures are in degrees centigrade and the parts and percentages are by weight, unless designated as par-ts by volume. Where parts are by volume, the amount signifies the volume occupied by the same number of parts by weight of water at 4 C.

PREPARATION OF HALOGENATED RESBENZOPHENONES Example 1 A solution of 160 parts of bromine in 525 parts of glacial acetic acid was added dropwise over 1% to 2 hours to a cold solution of 214 parts of resbenzophenone f (2,4-dihydroxy-benzophenone) in 2100 parts of glacial acetic acid. The addition was made at temperatures between 10 and 16. The mass was permitted to warm up to ambient room temperature and then was diluted with 5000 parts of water while agitating the mixture. The resultant slurry was filtered and the filter cake of 5-bromo-2,4-dihydroxy-benzophenone (5 bromo-resbenzophenone) was washed with two portions of water of 250 parts each. The washed product, after drying in vacuo at 50, Weighed 262 parts (89.3% of the theoretical yield) and had a melting point of 117 to 122.

Analysis-Cale. for C H O Br: Br 27.26%. Found: Br 28.18%.

Examples 2 to 6 The bromination of 2,4-dihydroxybenzophenone was repeated in the following solvents, the conditions and other process details being as set out in Example 1. The results are set out in the following table.

Example 7 A solution of 160 parts of bromine in 262 parts of glacial acetic acid was added dropwise to a warm (35 to 40) solution of 107 parts of resbeuzophenone in 525 parts of glacial acetic acid. The temperature of the mass was maintained at 35 to 40 during the addition, which required between 1% and 2 hours. The resultant slurry was filtered and the filter cake of 3,5-dibromo-2,4-dihydroxy-benzophenone (3,S-dibromo-resbenzophenone) was washed with 250 parts of water, then with 250 parts of 5% aqueous sodium thiosulfate solution and finally with 250 parts of water. An additional quantity of the dibromo-compound was obtained by diluting the filtrate with about 1500 parts of water, filtering and washing as described above. The total yield of 3,5-dibromo-2,4 dihydroxy-benzophenone obtained, after being dried in vacuo at 50, amounted to- 166 parts (89% of the theoretical yield (of material melting at 148 to l50.5.

Analysis.-Calc. for C Il O Br Br 42.96%. Found: Br 41.5%, 42.0%.

Example 8 Chlorine was passed at a slow rate into a warm (30 to 35) solution of 53.5 parts of resbenzophenone in 525 parts of glacial acetic acid until 17.8 parts of chlorine had been absorbed. The resultant solution was agitated for /2 hour at 30 to 35, and then diluted with 500 parts of water. The slurry was filtered and the filter cake was washed with two portions of water of parts each. The washed cake was dried in vacuo at 50. The product, melting at 131 to 139, was a mixture of S-chloroand 3,5-dichloro-resbenzophenones.

On further dilution of the filtrate with about 1000 parts of water, filtering and washing, an additional product was obtained, melting at 117 to 128. It was essentially 5-chloro-resbenzophenone containing some unchlorinated resbenzophenone.

Example 9 A solution of 168 parts of bromine in 525 parts of glacial acetic acid was added dropwise to a warm (30 to 35) solution of 228 parts of 2-hydroxy-4-methoxybenzophenone in 1049 parts of glacial acetic acid. The resultant slurry was agitated for 2 hours after the addition was complete and then the mixture was permitted to stand for about 16 hours without further temperature control. The resultant slurry was filtered and the filter cake was washed with 500 parts of water, then with 250 parts of 5% aqueous sodium thiosulfate solution and lastly with 500 parts of water. An additional quantity of productwas obtained by diluting the filtrate with 220 parts of water, vigorously agitating the mixture, filtering the resultant slurry, and washing as indicated above. The filter cakes were combined and dried in vacuo at 50". Thus there were obtained 148 parts (50% of the theoretical yield) of 5-bromo-Z-hydroxy-4-methoxy-benzophenone having a melting point of 127.8 to 128.2.

Analysis-Cale. for C H O Br: Br 26.02%. Found: Br 25.95%, 26.23%.

Mixed melting point determination made with the product of this example and the product obtained by methylating 5-bromo-resbenzophenone, as described be low, showed the identity of the two products.

The methylation was carried out as follows: 13.2 parts of dimethyl sulfate were added dropwise over the course of a half-hour to a warm (40) solution of 29.3 parts of S-bromo-resbenzophenone (prepared as described in Example 1 above) in 29 parts of aqueous sodium hydroxide containing 4 parts of caustic soda, while maintaining the temperature of the mixture between 30 and 40. After addition of the dimethyl sulfate, about 50 parts of water were added to permit the resulting slurry to be more easily agitated, and the mixture was agitated for 2 /2 hours and then rendered acid to Congo red by the addition of dilute hydrochloric acid. The slurry was filtered. On being recrystallized from aqueous acetone, the product (5-bromo-2-hydroxy-4-methoxy-benzophenone) melted at 124 to 127.

Example A solution of 320 parts of bromine in 525 parts glacial acetic acid was added to a hot (60") solution of 228 parts of 2-hydroxy-4-methoxy-benzophenone in 1674 parts of glacial acetic acid. The addition was carried out at 60 to 65 and the mixture was maintained at said temperature for 2 hours after the bromine had been added.

Two products were obtained by fractional precipitation on gradual dilution of the reaction mixture with water. The first fraction, containing 35% bromine and melting at 74 to 85 was a mitxure of 5-bromoand 3,5-dibromo- Z-hydroxy-4-methoxy-benzophenones. The second fraction, containing 40.3% Br (theory for dibromo=41.4% Br) and melting at 93 to 96, was 3,5-dibromo-2-hyd1 oxy-4-methoxy-benzophenone.

Example 11 Gaseous chlorine was passed into a solution of 57 parts of 2-hydroxy-4-methoxy-benzophenone in 525 parts of glacial acetic acid, maintained at 35 until 18.8 parts of chlorine had been absrobed. The mass was agitated at 30 to for /2 hour after the addition was complete and then 150 parts of water were added. The resultant slurry was filtered and the filter cake of 5-chloro-2-hydroxy-4-methoxy-benophenone was washed with two portions of water, each of 100 parts. The washed cake was driedin vacuo at An additional quantity of product was obtained by diluting the mother liquor with 250 parts of water.

Example 12 Twenty-five parts of dodecyl-bromide were added dropwise, over about /2 hour, to a refluxing mixture of 29.3 parts of 5-bromo-2,4-dihydroxy-benzophenone, 4 parts of sodium hydroxide and 75 parts of obsolute ethanol. The mixture was maintained refluxing for 7 hours thereafter and then agitated, without further heating, for about 6 hours. The resulting solution was rendered alkaline to litmus by the addition of caustic soda and then poured into 2500 parts of water, and the resulting precipitate of 5-bromo-4-dodecoxy-Z-hydroxy-benzophenone was separated by filtration. The crude 5-bromo-4-dodecoxy-2-hydroxy-benzophenone was recrystallized from glacial acetic acid. The purified product melted at 77 to 83 and contained 16.7% Br (theory=17.3%).

The efiectiveness of a compound as an absorber of ultraviolet rays is based in the first instance on its ability to screen out the destructive ultraviolet rays in the near region; namely, from 350 mm to 400 m which is considered to be the practical range of ultraviolet radiation reaching the earths surface from the sun.

To test the eflfectiveness of the halogenated hydroxybenzophenone compounds employed as stabilizers against the deleterious action of ultraviolet light in accordance with the present invention, the absorbency for ultraviolet light of solutions of compounds prepared in accordance with the above examples was measured in a standard spectrophotometer (Carey Model 11 Spectrophotometer) and compared with that of like solutions of related compounds sold commercially, or heretofore proposed, for the purpose. Readings were taken from 400 m down to 350 m The tests were carried out with solutions in methyl alcohol of the following compounds at a concentration of 25 milligrams of the compound per cc.

Compound No. Composition The results are set out in Table II, below.

TABLE II [Percent absorption between 350 and 400 m Wave length in my Compound No.

STABILIZATION OF LIGHT SENSITIVE COMPOSI- TIONS BY MEANS OF HALOGENATED RESBEN- ZOPHENONES In order to determine the effectiveness of the halogenated resbenzophenones and related compounds of this invention to protect resinous compositions containing them against the deleterious effects of ultraviolet light, they were incorporated in small amounts into resinous compositions which are known to be adversely eifected by ultraviolet light and the stabilizing effect on the compositions was determined by exposure in a Fade-Ometer.

The resinous compositions (prepolymers) employed were prepared as follows.

POLYESTER-STYRENE RESINS Resin A. Tetrabromo-phthalic anhydride resin.A mixture of 233.4 parts of diethyleneglycol, 98 parts of maleic acid anhydride, 59.2 parts of phthalic acid anhydride and 278.4 parts of tetrabromo-phthalic acid anhydride was heated under reflux in an inert atmosphere at 175 until the acid number of the mass was reduced to about 65. The mass was cooled to and then added to 276 parts of styrene (containing a small amount of hydroquinone as a stabilizer), and the mixture was cooled as rapidly as possible to prevent premature gelation.

Resin B. Tetrachloro-phthalic anhydride resin.A similar prepolymer was prepared using 172 parts of tetrachlorophthalic acid anhydride in place of the tetrabromophthalic acid anhydride in the above process for making Resin A. Heating was continued until an acid number of 63.0 was obtained. The polyester mass was cooled to 140 and added to 230 parts of styrene (containing hydroquinone as stabilizer), and the mixture was cooled as quickly as possible, to prevent premature gelation.

Resin C. Hexachloro "Nadic anhydride resin.--A polyester-styrene prepolymer mixture was made using 233 parts of hexachloro Nadic anhydride (1,4,5,6,7,7- hexachloroendo cis bicyclo-[2,2,1]5-heptene-2,3-dicarboxylic acid anhydride) in place of the tetrabromophthalic acid anhydride in the above process for making Resin A. Heating at to 175 was continued until an acid number of about 40 was obtained. The polyester mass was cooled to 140 and added to 252 parts of styrene (con taining a stabilizing amount of hydroquinone) and the resulting mixture was cooled rapidly to prevent premature gelation.

Example 14 The test procedure of Example 13 was repeated with and without Compound 1 (S-bromo-2,4-dihydroxy-benzophenone) with the addition to the prepolymer resins Resin D. Tetrachlorophthalic acid anhydride resin con- 5 e a raining no phthalic anhydride.-A similar polyester sty- 35 33 of Vanous oramc dyestuffs as colonng agents rene mixture was prepared using 286 parts of tetrachlorophthalic acid anhydride in place of the phthalic and Bnnlfmt O11 B111? EMA unsymmetrlcal 1,4-d1a1k3/1' tetrabromophthalic acid anhydrides used in the above ammoimlhmqmmm dyestufi of process for making Resin A. Heating at 170 to 175 was Q F B1216 BL C0110 continued until an acid number of 66 was obtained. The (211111011116 Yellow Base polyester mass was cooled to 105 and 249 parts of sty- In the absence of the stabilizer, exposure of the cured rene (containing a stabilizing amount of hydroquinone) colored resins in the Fade-Ometer resulted in fading of was added. The mixture was cooled rapidly to prevent the color. In contrast thereto, exposure of the cured premature gelation. 15 colored resins containing 1% of Compound 1 for a like Resin E. Hexachloro Nadic anhydride resin containperiod in the Fade-Ometer produced very little fading; ing n0 phthalic anhydride.--A polyester-styrene prepolythe im rovement in light-stability was clearly evident. mer mixture was made using 371.2 parts of hexachloro Example 15 7 Nadic anhydride in place of the phthalic and tetra- Add.tional com t t d bromo phthalic acid anhydrides in the above process for t a 1 para 68 were cal-me out W1 making Rasin Heating at to 1750 was com tut, above polyester-styrene I'SSIDS to evaluate the dicetinned until an acid numbzf of 61 was obtained The tiveness of the various stabilizers on a molecularly equivpolyester mass was cooled to 100 and 285 parts of styallent g i 'g of i 3 rene (containing a stabilizing amount of hydroquinone) g n e 2. 3 1 i f was added and the resulting mixture was cooled rapidly Cnzop enone)? w as t e owest m0 ecu at f to prevent premature gelation' 1% of the weight of the prepolymer was employed; in Comparative tests were carried out with Said prepoly the cases of the other stabillzers tested, a molecularly mers containing halogenated hydroxy-benzophenones as y g g i The results are Set stabilizers in accordance with the present invention, with on m es an e no stabilizer (blank), and with commercially available or TABLE IV-WRESIN A previously proposed stabilizers. Stabilizer e i discolql'ation One set of tests was carried out in the following mancompound No. ggg g gg Blank Considerable.

Example 13 8 do. To 10 parts of polyester-styrene prepolymer prepared i g as described above (Resin A, B or C), 0.1 part of the 11 A I stabilizer to be tested was added and dissolved by hea 12 pgreclab ing on a steam bath. A few drops of a commercial polym- 1 erization catalyst comprising methylethyl ketone peroxide 40 4 (Lupersol DDM) were added, and the mixture was cast 6 in a film inch thick. "'i

The film was permitted to stand at ambient temperature 011 i116 b21513 of Visual examination of the Lest P q for 4 hours and then cured at 90 for 10 hours. after xp t ey ranked t in the r r f The cured films were placed in the Fade-Ometer and dficfeaslng effectiveness of StablllZBfI exposed for 100 hours. The exposed films were inspected 4 12 1 11 10 9 for color change. The results obtained are set out 111 TABLE V REISIN D the Table III below, wherein the extent of discoloration 1s evaluated according to the following scale: Extent of discoloration after exposure none in Fade-Ometcr neg ligib 1e Stalnlrzer compound No. very Slight 20 hours hours Slight Bl k G 1 bl V an n t nan. 5. 3-

16 ivl li 't conslderable 11. sli g lit ag igi bie. strong n LNMdemte gloisideurable.

. ("1P 0 GT3 0. very strong 4. rln Slight. As shown by the blank test, discoloration (yellowing) 9 of the resin occurred in the absence of a stabilizer. 60

TABLE III Extent of discoloration Stabilizer compound No.

Resin A. Resin B Resin 0 None (blank) Strong Appreciable. 11 do Very slight. 8 do D0. 1 Slight to moderate None. 9 Moderate rln Do, 3 rln Slight bleaching e. Do. 4 Slight to moderate None Do. 5 Moderate dn D0, 7 Slight to moderate Slight bleaching Do.

On the basis of visual examination of the test plaques after exposure, they ranked as follows, in the order of decreasing effectiveness of stabilizer:

Extent of discoloration after 200 hours exposure in Fade-Ometer Stabilizer compound No.

On the basis of visual examination of the test plaques after exposure, they ranked as follows, in the order of decreasing elfectiveness of stabilizer:

POLYVINYL CHLORIDE RESIN Test films of plasticized polyvinyl chloride, with and without stabilizers, were prepared and tested as set out below. This resin is subject to pitting and discoloration (yellowing) by ultraviolet light in the absence of a stabilizer.

Example 16 Fifty parts of polyvinyl chloride, 25 parts of dioctylphthalate and 284 parts of cyclohexanone were mixed together, with and Without the addition of /2 part of stabilizer. Films of the resulting compositions were drawn on a glass plate, using a blade setting of 0.075 inch. The films were permitted to set at ambient temperature for about 16 hours, and the residual solvent was removed by heating the films in an oven for 3 days. The average thickness of the resulting films as determined by a micrometer was 0.015 inch in each instance. The films were exposed in a Fade-Ometer. The results are set out in Table VII below. As an indication of the relative effectiveness of the stabilizers it is noted that afterexposure for 160 hours, the film without stabilizer (Blank) was brown and very badly pitted; the film stabilized with Compound 8 was less brown but very badly pitted; and the films stabi lized with Compounds 1 and 4 were only a slight yellow in color and were only faintly pitted.

10 invention as compared with compounds heretofore proposed for the purpose.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative examples and that changes can be made without departing from the scope of the invention.

Thus, various compositions and materials subject to deterioration by ultraviolet light can be rendered resistant to ultraviolet light by having a minor amount of a 2- hydroxy-benzophenone of the type set out above incorporated therewith or into a coating applied thereto. Thus, they include various organic plastics, resins, perfumes, foodstulfs and the like. Polyester resinous compositions are particularly important, and especially the class of copolymer resins disclosed in U.S.P. 2,777,828.

Polyolefine compositions, and especially polyethylene and polypropylene, are additional exemplifications of materials subject to the harmful effects of ultraviolet radiation which are benefited by the protective action of the 2-hydroxy-benzophenones employed as ultraviolet stabilizers in accordance with the present invention. For example, by incorporating with polyethylene or poly propylene 0.01% to 5% of the weight thereof of a 2 hydroxybenzophenone having the formula wherein R, X and Y have the above meaning excellent protection against the deteriorating effect of ul traviolet radiation is obtained, as illustrated by the following specific example.

Example 17 Polypropylene was impregnated with 5-bromo-2-hydroxy-4-dodecoxy-benzophenone (Compound No. 5 above) by milling a mixture of the polypropylene with 1.0% of its weight of the S-bromo-2-hydroxy-4-dodecoxybenzophenone for five minutes at .185 C. on a 2-r-oll mill. The milled sheet was cut up and molded at 250 C. into IO-mil sheets. The molded sheets were exposed to artificial ultraviolet radiation equivalent to 720 foot-candles in intensity.

Measurement of the physical properties of the resulting On the basis of visual examination of the test films after exposure, they ranked as follows, in the order of decreasing effectiveness of stabilizer:

4 5 2 1 3 7 11 8 The results of these tests show the beneficial effect of the compounds employed in accordance with the present invention as inhibitors of the deleterious action of ultraviolet light, and especially the surprising superiority of the compounds employed in accordance with the present polypropylene sheets, as compared with similar sheets of polypropylene containing no additive, showed that the polypropylene sheets containing the added stabilizer retained their original elongation and tensile strength for a much greater period of time and required a very much. longer exposure for substantial deterioration in these properties.

Similarly, a polyethylene sheet having improved resistance to ultraviolet light is produced by milling polyethylene With 0.1% of its weight of 5-bromo-4 dodecoxy 2-hydroxy benzophenone and forming the resulting composition into a film 0.014 inch thick.

Various plasticizers and catalysts may be employed in conjunction with the resinous compositions illustrated in the above specific examples, a number of which are well known in the art.

The stabilizers of this invention can be used to protect against, or otherwise retard the deterioration due to, ultraviolet light of other colorless or colored resinous materials, such as, melamine-formaldehyde resins, nylon, phenolics, acrylates and methacrylates, vinyl and vinylidine polymers and copolymers, cellulose organic esters, regenerated cellulose, epoxy resins (copolymers of bisphenols and epoxy compounds) and the like. The so stabilized products can be fabricated into the desired form by molding, extruding or laminating.

The stabilized light sensitive compositions of this invention may and usually do contain other ingredients, such as fillers, polymerization inhibitors, extenders, mold lubricants, spinning assistants, solvents, plasticizers and the like. The formulation, curing and application treatment of such compositions are well known to those skilled in the art to which the specific compositions pertain and accordingly require no extended discussion.

We claim:

1. A resinous material which is normally subject to deterioration by ultraviolet light and as a stabilizer therehibitor of the deleterious action of ultraviolet light, 0.01% a 2-hydroxy-benzophenone having the formula:

WQL

wherein R is selected from the group consisting of hydrogen and alkyl,

X is selected from the group consisting of bromine and chlorine, and

Y is selected from the group consisting of hydrogen,

bromine and chlorine.

2. A polyester-styrene resin composition derived from a, polycarboxylic acid, an aliphatic polyhydric compound and styrene having incorporated therewith, as an inhibitor of the deleterious action of ultraviolet light, 0.01% to 5.0% of its weight of a Z-hydroxy-benzophenone defined in claim 1.

3. A polyvinyl chloride resin composition having incorporated therewith, as an inhibitor of the deleterious action of ultraviolet light, 0.01% to 5.0% of its weight of a 2-hydroxy-benzophenone defined in claim 1.

4. A polyester resin composition derived from a polycarboxylic acid and an aliphatic polyhydric compound having incorporated therewith, as an inhibitor of the deleterious .action of ultraviolet light, 0.01% to 5.0% of its weight of a 2-hydroxy-benzophen'one defined in claim 1.

5. A polyethylene composition having incorporated therewith, as an inhibitor of the deleterious action of ultraviolet light, 0.01% to 5.0% of its weight of a 2-hydroxy-benzophenone defined in claim 1.

6. A polypropylene composition having incorporated therewith, as an inhibitor of the deleterious action of ultraviolet light, 0.01% to 5.0% of its Weight of a Z-hydroxy-benzophenone defined in claim 1.

7. A material which is normally subjected to deterioration by ultraviolet light and selected from the group consisting of polyester resins derived from polycarboxylic acids and aliphatic polyhydric compounds, polyesterstyrene resins derived from polycarboxylic acids, aliphatic polyhydric compounds and styrene, polyvinyl chloride, polyvinyl acetate, polyethylene and polypropylene having incorporated therewith, as a stabilizer therefor, 0.1% to 5% of its weight of S-bromo-2,4-dihydroxy-benzophenone.

8. A material which is normally subject to deterioration by ultraviolet light and selected from the group consisting of polyester resins derived from polycarboxylic-acids and aliphatic polyhydric compounds, polyester-styrene resins derived from polycarboxylic acids, aliphatic polyhydric compounds and styrene, polyvinyl chloride, polyvinyl acetate, polyethylene and polypropylene having incorporated therewith, as a stabilizer therefor, 0.1% to 5% of its weight of 3,5-dibromo-2,4-dihydroxy-benzophenone.

9. A material which is normally subject to deterioration by ultraviolet light and selected from the group consisting of polyester resins derived from polycarboxylic acids and aliphatic polyhydric compounds, polyester-styrene resins derived from polycarboxylic acids, aliphatic polyhydric compounds and styrene, polyvinyl chloride, polyvinyl acetate, polyethylene and polypropylene having incorporated therewith, as a stabilizer therefor, 0.1% to 5% of its weight of 4-all oxy5-bromo-2-hydroxy-benzm phenone having 1 to 12 alkyl carbon atoms in the alkoxy group.

10. A material which is normally subject to deterioration by ultraviolet light and selected from the group consisting of polyester resins derived from polycarboxylic acids and aliphatic polyhydric compounds, polyesterstyrene resins derived from polycarboxylic acids, aliphatic polyhydric compounds and styrene, polyvinyl chloride, polyvinyl acetate, polyethylene and polypropylene having incorporated therewith, as a stabilizer therefor, 0.1% to 5% of its weight of 4-dodecoxy-5-bromo-2-hydroxy-benzophenone.

11. A material which is normally subject to deterioration by ultraviolet light and selected from the group consisting of polyester resins derived from polycarboxylic acids and aliphatic polyhydric compounds, polyesterstyrene resins derived from polycarboxylic acids, aliphatic polyhydric compounds and styrene, polyvinyl chloride, polyvinyl acetate, polyethylene and polypropylene having incorporated therewith as a stabilizer therefor, 0.1% to 5% of its Weight of 4-alkoxy-5-chloro-2-hydroxy-benzophenone having 1 to 12 alkyl carbon atoms in the alkoxy group.

References Cited by the Examiner UNITED STATES PATENTS 2,831,017 4/58 Senkbeil 260-591 2,861,053 11/58 Lappin et al. 260591 2,892,872 7/59 Foster 260591 OTHER REFERENCES Dalvi et al., Jo. Ind. Chem. Soc., vol. 33 (1956), 260591.

LEON J. BERCOVITZ, Primary Examiner.

MILTON STERMAN, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3,192,179 June 29, 1965 Sydney M. Spatz et al.

It is hereby certified that error appears in the above numbered petent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 4 for "radial" read radical column 3, line 25, for "derivatives" read derivative column 4, line 30, for "yield (of" read yield) of column 5, line 26, for "mitxure" read mixture line 36, for "absrobed" read absorbed line 49, for "obsolute" read absolute line 51, for "6" read l6 column ll, line 28, strike out "hibitor of the deleterious action of ultraviolet light, 0n0l%" and insert instead for against such deterioration a stabilizing amount of column 12, line 1, for "subjected" read subject Signed and sealed this 15th day of March 1966.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. A RESINOUS MATERIAL WHICH IS NORMALLY SUBJECT TO DETERIORATION BY ULTRAVIOLET LIGHT AND AS A STABILIZER THEREHIBITOR OF THE DELETERIOUS ACTION OF ULTRAVIOLET LIGHT, 0.01% A 2-HYDROXY-BENZOPHENONE HAVING THE FORMULA: 